CN112480664B - Polyamide material, automobile cooling hose and preparation method thereof - Google Patents
Polyamide material, automobile cooling hose and preparation method thereof Download PDFInfo
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- CN112480664B CN112480664B CN202011377149.3A CN202011377149A CN112480664B CN 112480664 B CN112480664 B CN 112480664B CN 202011377149 A CN202011377149 A CN 202011377149A CN 112480664 B CN112480664 B CN 112480664B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a polyamide material, an automobile cooling hose and a preparation method thereof, wherein the polyamide material comprises the following raw materials in parts by weight: 60-80 parts of nylon 66,5-10 parts of long-chain nylon, 10-30 parts of toughening agent, 0.5-3 parts of hydrolysis resistance agent and 0.1-2 parts of auxiliary agent; the toughening agent includes a combination of an ethylene-1-octene copolymer and a maleic anhydride grafted ethylene-1-octene copolymer. The polyamide material provided by the invention takes the nylon 66 as a main material, so that the use of high-cost long-chain nylon is greatly reduced, the polyamide material taking the nylon 66 as the main material has hydrolysis resistance and high flexibility due to the addition of the toughening agent and the hydrolysis resistance, and meanwhile, the invention creatively discovers that the polyamide material can be prepared by an extrusion molding process, so that the automobile cooling hose with less service performance attenuation under the working condition of long-term contact with cooling liquid can be obtained.
Description
Technical Field
The invention relates to the technical field of cooling hoses, in particular to a polyamide material, an automobile cooling hose and a preparation method thereof.
Background
At present, a water-cooling pipe, a warm air nylon pipe, a motor cooling pipe and the like of an automobile battery are mostly made of long-chain nylon materials such as nylon 11, nylon 612, nylon 12 and the like, however, the materials are high in cost, and meanwhile, the problems that performance attenuation is obvious in the long-term use process and the like exist. The nylon 66 material has excellent mechanical strength, fatigue strength and heat resistance, and is low in price and wide in application, but the nylon 66 material has the problems of insufficient toughness and poor hydrolysis resistance, so that the application of the nylon 66 material in an automobile cooling hose is limited.
CN109504080A discloses a hydrolysis-resistant reinforced nylon and a preparation method thereof, wherein the disclosed nylon is prepared from the following raw materials in parts by weight: 58-68 parts of nylon, 2-7 parts of a toughening agent, 31-35 parts of glass fiber, 0.1-0.3 part of an antioxidant, 0.05-0.15 part of a silane coupling agent KH560, 0.2-0.7 part of an anti-hydrolysis agent, 0.2-0.7 part of an ethylene-acrylic acid copolymer and 2-3 parts of beta-cyclodextrin. The reinforced nylon disclosed by the method has the main advantages of good hydrolysis resistance and capability of meeting the processing requirements of an automobile water chamber, but the reinforced nylon is not made of nylon 66 as a main material and is expensive.
CN100432145C discloses a toughened nylon using maleic anhydride grafted ethylene-1-octene copolymer as a toughening agent and a preparation method thereof. The disclosed nylon comprises the following components in percentage by weight: 60-90% of nylon, 10-30% of maleic anhydride grafted ethylene-1-octene copolymer and 0-10% of polyolefin, wherein the sum of the percentages of the components is 100%, and 0.02-2% of auxiliary agent is added, and the auxiliary agent is calcium stearate or stearic acid. The nylon adopts maleic anhydride grafted ethylene-1-octene copolymer as a toughening agent, and reduces the strength reduction amplitude of the nylon alloy due to the addition of the second component while achieving the same toughening effect. However, the disclosed nylon has relatively poor hydrolysis resistance and poor extrusion molding capability, and cannot meet the requirements of automobile cooling hoses.
In view of the above, it is important to develop a polyamide material that satisfies the requirements of the cooling hose for automobiles and has good hydrolysis resistance, heat resistance, flexibility and extrudability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyamide material, an automobile cooling hose and a preparation method thereof, wherein the polyamide material has better hydrolysis resistance, heat resistance, flexibility and extrudability, and the prepared automobile cooling hose has smaller service performance attenuation under the working condition of long-term contact with cooling liquid.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polyamide material, which comprises the following raw materials in parts by weight: 60-80 parts of nylon 66,5-10 parts of long-chain nylon, 10-30 parts of toughening agent, 0.5-3 parts of hydrolysis resistance agent and 0.1-2 parts of auxiliary agent;
the toughening agent includes a combination of ethylene-1-octene copolymer (POE) and maleic anhydride grafted ethylene-1-octene copolymer (POE-g-MAH).
The polyamide material takes the nylon 66 as a main material, so that the use of high-cost long-chain nylon is greatly reduced, the polyamide material taking the nylon 66 as the main body has hydrolysis resistance and high flexibility due to the addition of the toughening agent and the hydrolysis resistance, and the polyamide material can be prepared by an extrusion molding process, so that the polyamide material which has less service performance attenuation under the working condition of long-term contact with cooling liquid and can meet the use requirement of the conventional automobile cooling hose is innovatively discovered.
The toughening agent is the combination of POE and POE-g-MAH, and the POE-g-MAH can be used as the toughening agent and the compatilizer to improve the compatibility of the auxiliary agents such as the toughening agent and the like and the nylon 66, so that the uniformity of the blending material and the toughness and melt fluidity of the material are greatly improved, and the polyamide material of which the main component is nylon 66 has better extrudability.
The POE-g-MAH can be a commercially available product or a self-made product, and the preparation method of the POE-g-MAH comprises the following steps: the POE-g-MAH material with the grafting rate of more than 8 percent is obtained by adopting a solution grafting method, using dicumyl peroxide as an initiator and MAH as a monomer to react for 5 hours at the temperature of 150 ℃.
The nylon 66 is 60-80 parts by weight, such as 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts and the like.
The weight portion of the long-chain nylon is 5-10 parts, such as 6 parts, 7 parts, 8 parts, 9 parts and the like.
The weight portion of the toughening agent is 10-30 portions, such as 12 portions, 14 portions, 16 portions, 18 portions, 20 portions, 22 portions, 24 portions, 26 portions, 28 portions and the like.
The hydrolysis-resistant agent is 0.5-3 parts by weight, such as 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts and the like.
The assistant is 0.1-2 parts by weight, such as 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts and the like. The auxiliary agent refers to other auxiliary agents except for a toughening agent and a hydrolysis resistance agent.
Preferably, the weight ratio of POE and POE-g-MAH is 1.
According to the invention, the POE and the POE-g-MAH in a specific ratio can well play a synergistic effect, the POE material is a toughening agent with excellent performance, but the POE material has poor compatibility with a nylon 66 material, the content of the POE can be increased by adding the POE-g-MAH to further toughen the nylon 66 material, and the POE-g-MAH serving as a better compatilizer can be fully mixed with the nylon 66 material, so that the polyamide material has good toughness, melt flowability and extrudability. When the weight ratio of the POE to the POE-g-MAH is too high, namely, when the content of the POE in the toughening agent is higher, the compatibility of the nylon 66 and auxiliaries such as the toughening agent is poor, so that the material performance is not uniform, and the extrudability of the material is not facilitated; when the weight ratio of POE to POE-g-MAH is too low, i.e. the content of POE in the toughening agent is too low, the nylon 66 can not be effectively toughened, and the extrudability of the material is also affected.
Preferably, the long chain nylon comprises any one of nylon 11, nylon 612, nylon 12, or nylon 1010, or a combination of at least two thereof, with typical but non-limiting combinations comprising: a combination of nylon 11 and nylon 612, a combination of nylon 612, nylon 12, and nylon 1010, a combination of nylon 11, nylon 612, nylon 12, and nylon 1010, and the like.
The long-chain nylon in the invention refers to a nylon material with a continuous carbon chain length of more than 10 in a nylon molecule.
Preferably, the hydrolysis resistance agent comprises polycarbodiimide.
In the invention, the N = C = N functional group in the polycarbodiimide has very high activity, and can preferentially react with terminal carboxyl, terminal hydroxyl and water molecules in a polyamide material system, so that the contact of the water molecules and trace acid with nylon 66 molecular chains is avoided, the probability of occurrence of catalytic decomposition reaction is reduced, and the hydrolysis resistance of the material can be better improved by adding the polycarbodiimide.
Preferably, the polycarbodiimide grade includes any one or a combination of at least two of HYDROSTATA 2, bio-SAH 382N, S-9000, or S-7000, with typical but non-limiting combinations including: a combination of HYDROSTAB 2 and Bio-SAH 382N, a combination of Bio-SAH 382N, S-9000 and S-7000, a combination of HYDROSTAB 2, bio-SAH 382N, S-9000 and S-7000, and the like.
Preferably, the polycarbodiimide has a molar content of N = C = N functional groups of 10% to 20%, such as 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc.
Too high a content of N = C = N functional groups leads to excessive crosslinking of the nylon 66 material, which is detrimental to the extrusion of the polyamide material, and too low a content of N = C = N functional groups leads to poor hydrolysis resistance of the material.
Preferably, the auxiliaries comprise antioxidants and/or processing aids.
Preferably, the antioxidant comprises n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076) and/or 3- (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168), preferably a combination of antioxidant 1076 and antioxidant 168.
Preferably, the antioxidant is present in an amount of 0.1 to 1 part by weight, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, and the like.
Preferably, the processing aid is present in an amount of 0.1 to 1 part by weight, such as 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, and the like.
Preferably, the polyamide material comprises the following raw materials in parts by weight: 60-80 parts of nylon 66,5-10 parts of long-chain nylon, 10-30 parts of toughening agent, 0.5-3 parts of hydrolysis resistance agent, 0.1-1 part of antioxidant and 0.1-1 part of processing aid.
The nylon 66 is 60-80 parts by weight, such as 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts and the like.
The weight portion of the long-chain nylon is 5-10 portions, such as 6 portions, 7 portions, 8 portions, 9 portions and the like.
The weight portion of the toughening agent is 10-30 portions, such as 12 portions, 14 portions, 16 portions, 18 portions, 20 portions, 22 portions, 24 portions, 26 portions, 28 portions and the like.
The hydrolysis resistant agent is 0.5-3 parts by weight, such as 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts and the like.
The antioxidant is 0.1-1 part by weight, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and the like.
The processing aid is 0.1-1 part by weight, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and the like.
As a preferred technical scheme, the polyamide material comprises the following raw materials in parts by weight: 70-75 parts of nylon 66,5-10 parts of long-chain nylon, 12-29 parts of toughening agent, 1.5-2.5 parts of hydrolysis resistance agent, 0.2-1 part of antioxidant and 0.5-1 part of processing aid.
The nylon 66 is 60-80 parts by weight, such as 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts and the like.
The weight portion of the long-chain nylon is 5-10 portions, such as 6 portions, 7 portions, 8 portions, 9 portions and the like.
The weight portion of the toughening agent is 10-30 portions, such as 12 portions, 14 portions, 16 portions, 18 portions, 20 portions, 22 portions, 24 portions, 26 portions, 28 portions and the like.
The hydrolysis resistant agent is 1.5-2.5 parts, such as 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts and the like.
The antioxidant is 0.1-1 part by weight, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and the like.
The processing aid is 0.1-1 part by weight, such as 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part and the like.
As a further preferable technical scheme, the polyamide material comprises the following components in parts by weight: 70-75 parts of nylon 66,5-10 parts of long-chain nylon, 7-15 parts of POE,5-14 parts of POE-g-MAH,1.5-2.5 parts of hydrolysis resistance agent, 0.1-0.5 part of antioxidant 1076,0.1-0.5 part of antioxidant 168 and 0.5-1 part of processing aid.
The nylon 66 is 70-75 parts by weight, such as 71 parts, 72 parts, 73 parts, 74 parts and the like.
The weight portion of the long-chain nylon is 5-10 parts, such as 6 parts, 7 parts, 8 parts, 9 parts and the like.
The POE is 7-15 parts by weight, such as 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and the like.
The POE-g-MAH is 5-14 parts by weight, such as 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts and the like.
The hydrolysis-resistant agent is 1.5-2.5 parts by weight, such as 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts and the like.
The antioxidant 1076 is 0.1-0.5 part by weight, such as 0.2 part, 0.3 part, 0.4 part and the like.
The antioxidant 168 is 0.1-0.5 part by weight, such as 0.2 part, 0.3 part, 0.4 part and the like.
The processing aid is 0.1-0.5 part by weight, such as 0.2 part, 0.3 part, 0.4 part and the like.
The polyamide material can be obtained according to a conventional nylon material preparation method, namely, nylon 66, long-chain nylon, a toughening agent, a hydrolysis resistance agent and an auxiliary agent in formula amount are mixed and dried, and then the polyamide material is prepared by the preparation processes of extrusion, cooling, dehumidification, grain cutting, drying and the like.
In a second aspect, the invention provides an automobile cooling hose, and the raw materials for preparing the automobile cooling hose comprise the polyamide material of the first aspect.
In a third aspect, the present invention provides a method for preparing the automobile cooling hose of the second aspect, wherein the method comprises the following steps: and drying, continuously extruding, shaping, cooling, blow-drying, drawing and cutting the polyamide material to obtain the cooling hose.
Preferably, the temperature of the polyamide material is dried at 100-120 ℃, such as 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ and the like.
Preferably, the drying time of the polyamide material is 4-8h, such as 5h, 6h, 7h, etc.
Preferably, the continuous extrusion is carried out in an extruder.
Preferably, the temperature of one zone of the continuous extrusion is 220-260 ℃, such as 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃ and the like.
The invention innovatively provides various parameters of an extrusion processing technology for preparing a polyamide material with nylon 66 as a main material, the temperature of the first zone is in the range of 220-260 ℃, the high temperature can cause the low melt strength and the high flow rate of the material, which are not beneficial to shaping of a hose, the high temperature can also cause the aging and degradation of the material, and the low temperature can cause the high melt strength and the non-beneficial melt mixing of the material, which have an influence on the extrusion uniformity of the subsequent material.
Preferably, the temperature of the two zones of the continuous extrusion is between 260 ℃ and 270 ℃, such as 261 ℃, 262 ℃, 263 ℃, 264 ℃, 265 ℃, 266 ℃, 267 ℃, 268 ℃, 269 ℃ and the like.
The temperature of the two zones is in the temperature range of 260-270 ℃, the material is aged and degraded due to overhigh temperature, and the further melting of the material is influenced due to overlow temperature of the two zones.
Preferably, the temperature of the three zones of the continuous extrusion is 265-275 deg.C, such as 266 deg.C, 267 deg.C, 268 deg.C, 269 deg.C, 270 deg.C, 271 deg.C, 272 deg.C, 273 deg.C, 274 deg.C, 275 deg.C, etc.
The temperature of the three zones is in the range of 265-275 ℃, aging and degradation of the material can be caused by overhigh temperature, and the melt flowability of the material is insufficient by overlow temperature of the three zones, so that continuous extrusion of subsequent pipes is not facilitated.
Preferably, the temperature of the four zones of the continuous extrusion is 265-280 ℃, such as 262 ℃, 264 ℃, 266 ℃, 268 ℃, 270 ℃, 271 ℃, 272 ℃, 273 ℃, 274 ℃, 276 ℃, 278 ℃ and the like.
The temperature of the four zones is in the temperature range of 265-280 ℃, the material is aged and degraded due to overhigh temperature, the performance of the extruded pipe is influenced, the continuous extrusion of the pipe is influenced due to overlow temperature of the four zones, and the appearance of the extruded pipe is greatly influenced.
Preferably, the continuous extrusion has a flange temperature of 270-280 ℃, such as 271 ℃, 272 ℃, 273 ℃, 274 ℃, 275 ℃, 276 ℃, 277 ℃, 278 ℃, 279 ℃, etc.
The temperature of the flange is 270-280 ℃, the material is aged and degraded due to overhigh temperature of the flange, and the appearance of the pipe is influenced due to overlow temperature of the flange.
Preferably, the head temperature of the continuous extrusion is 270-280 ℃, such as 271 ℃, 272 ℃, 273 ℃, 274 ℃, 275 ℃, 276 ℃, 277 ℃, 278 ℃, 279 ℃, etc.
The temperature of the machine head is in the range of 270-280 ℃, the problem that the material is low in melt strength and easy to break in the traction process due to overhigh temperature of the machine head can be caused, the extrusion continuity is affected, and the problem that the melt strength is overlarge and the extrusion is slow due to overlow temperature of the machine head can be caused, and the appearance defect is easy to occur.
Preferably, the die temperature for the continuous extrusion is 270-280 ℃, such as 271 ℃, 272 ℃, 273 ℃, 274 ℃, 275 ℃, 276 ℃, 277 ℃, 278 ℃, 279 ℃, etc.
The temperature of the die is in the range of 270-280 ℃, the problem that the strength of a material melt is low and the material melt is easy to break in the traction process due to overhigh temperature of the die, the extrusion continuity is affected, and the problem that the melt strength is overlarge, the extrusion is slow and the appearance defect is easy to occur due to overlow temperature of the die.
Preferably, the extruder has a screw speed of 1000-2000r/min, such as 1100r/min, 1200r/min, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min, etc.
The too fast screw rod rotational speed can lead to the extrusion speed too fast, and the molten state of material is relatively poor, is unfavorable for the extrusion of tubular product, and the too slow screw rod rotational speed then can lead to the material to dwell time overlength in high temperature region, the phenomenon of ageing degradation appears easily.
Preferably, the rate of said drawing is 10-20m/min, such as 11m/min, 12m/min, 13m/min, 14m/min, 15m/min, 16m/min, 17m/min, 18m/min, 19m/min, etc.
The traction speed of the invention is too high, which can cause the mismatching of the integral extrusion speed and easily cause the problem of the fracture of the extruded pipe, and the traction speed is too low, which can influence the continuous extrusion speed.
As a preferred technical scheme, the preparation method comprises the following steps:
drying the polyamide material for 4-8h at the temperature of 100-120 ℃, and continuously extruding in an extruder with the screw rotating speed of 1000-2000r/min, wherein the temperature of each continuous extrusion section is as follows: the temperature of the first zone is 220-260 ℃, the temperature of the second zone is 260-270 ℃, the temperature of the third zone is 265-275 ℃, the temperature of the fourth zone is 265-280 ℃, the temperature of the flange is 270-280 ℃, the temperature of the head is 270-280 ℃ and the temperature of the die is 270-280 ℃, the automobile cooling hose is obtained by continuously extruding, then shaping, cooling and blow-drying, pulling at the speed of 10-20m/min and cutting.
According to the invention, by setting various process parameters of the extruder, the obtained polyamide material can better meet the use requirements of the automobile cooling hose, and particularly, the mutual matching of the temperatures of all sections is favorable for processing the automobile cooling hose with better comprehensive performance.
Compared with the prior art, the invention has the following beneficial effects:
the polyamide material takes the nylon 66 as a main material, so that the use of high-cost long-chain nylon is greatly reduced, the polyamide material taking the nylon 66 as the main body has hydrolysis resistance and high flexibility due to the addition of the toughening agent and the hydrolysis resistance, and the polyamide material can be prepared by an extrusion molding process, so that the polyamide material which has less service performance attenuation under the working condition of long-term contact with cooling liquid and can meet the use requirement of the conventional automobile cooling hose is innovatively discovered. The notch impact strength of the simply supported beam of the automobile cooling hose prepared from the polyamide material is more than 53.2H, the simply supported beam does not break when having no notch impact, and the strength retention rate is more than 79.8%.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a polyamide material, and the preparation raw materials of the polyamide material comprise the following components in parts by weight: 60 parts of nylon 66 (the mark is 50 BWFS), 10 parts of nylon 12 (the mark is 101L-NC 010), 7 parts of POE (the mark is DF 810), 14 parts of POE-g-MAH (the mark is GR 209), 1.5 parts of polycarbodiimide (the mark is HYDROSTATA 2, N = C = N functional group content is 17%), 0.5 part of antioxidant 1076 and 0.5 part of antioxidant 168.
The preparation method of the polyamide material comprises the following steps: mixing and drying nylon 66, long-chain nylon, a toughening agent, a hydrolysis resistance agent and an antioxidant according to respective parts by weight, and then preparing polyamide material granules by extrusion, cooling, dehumidification, grain cutting, drying and other preparation processes.
The embodiment also provides an automobile cooling hose taking the polyamide material as a raw material.
The preparation method of the automobile cooling hose comprises the following steps:
drying polyamide material granules for 4 hours at the temperature of 105 ℃, and continuously extruding in an extruder with the screw rotation speed of 1096r/min, wherein the temperature of each continuous extrusion section is respectively as follows: and the temperature of the first zone is 240 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 275 ℃, the temperature of the flange is 275 ℃, the temperature of the machine head is 273 ℃, the temperature of the die is 270 ℃, the automobile cooling hose is obtained by continuously extruding, shaping, cooling, blow-drying, drawing at the speed of 10.9m/min and cutting.
Example 2
The embodiment provides a polyamide material, and the preparation raw materials of the polyamide material comprise the following components in parts by weight: 70 parts of nylon 66 (with the mark of 103 HSL), 8 parts of nylon 612 (with the mark of CF-6S), 10 parts of POE (with the mark of 9061), 10 parts of POE-g-MAH (with the mark of GR 209), 1.5 parts of polycarbodiimide (N = C = N with the mark of Bio-SAH 382N, the content of functional groups is 10%), 0.3 part of antioxidant 1076 and 0.3 part of antioxidant 168.
The preparation method of the polyamide material comprises the following steps: mixing and drying nylon 66, long-chain nylon, a toughening agent, a hydrolysis resistance agent and an antioxidant according to respective parts by weight, and then preparing polyamide material granules by extrusion, cooling, dehumidification, grain cutting, drying and other preparation processes.
The embodiment also provides an automobile cooling hose taking the polyamide material as a raw material.
The preparation method of the automobile cooling hose comprises the following steps:
drying the polyamide material granules at the temperature of 110 ℃ for 5h, and continuously extruding in an extruder with the screw rotation speed of 1438r/min, wherein the temperature of each continuous extrusion section is respectively as follows: and the temperature of the first zone is 235 ℃, the temperature of the second zone is 265 ℃, the temperature of the third zone is 275 ℃, the temperature of the fourth zone is 275 ℃, the temperature of the flange is 280 ℃, the temperature of the head is 280 ℃, the temperature of the die is 275 ℃, the automobile cooling hose is obtained by continuously extruding, shaping, cooling and blow-drying, drawing at the speed of 15.3m/min and cutting.
Example 3
The embodiment provides a polyamide material, and the preparation raw materials of the polyamide material comprise the following components in parts by weight: 75 parts of nylon 66 (with the brand number of 103 FSL), 8 parts of nylon 11 (with the brand number of BESNOP40 TL), 10 parts of POE (with the brand number of H-5030S), 5 parts of POE-g-MAH (with the brand number of GR 209), 2 parts of polycarbodiimide (with the brand number of S-9000, N = C = N functional group content of 16%), 0.3 parts of antioxidant 1076 and 0.3 parts of antioxidant 168.
The preparation method of the polyamide material comprises the following steps: mixing and drying nylon 66, long-chain nylon, a toughening agent, a hydrolysis resistance agent and an antioxidant according to respective parts by weight, and then preparing polyamide material granules by extrusion, cooling, dehumidification, grain cutting, drying and other preparation processes.
The embodiment also provides an automobile cooling hose taking the polyamide material as a raw material.
The preparation method of the automobile cooling hose comprises the following steps:
drying the polyamide material granules for 6h at the temperature of 115 ℃, and continuously extruding in an extruder with the screw rotation speed of 1897r/min, wherein the temperatures of all sections in continuous extrusion are respectively as follows: and the temperature of the first zone is 245 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 270 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the flange is 275 ℃, the temperature of the machine head is 275 ℃, the temperature of the die is 275 ℃, the automobile cooling hose is formed after continuous extrusion, cooled, blow-dried, pulled at the speed of 18.6m/min and cut off, and the automobile cooling hose is obtained.
Example 4
The embodiment provides a polyamide material, which is prepared from the following raw materials in parts by weight: 80 parts of nylon 66 (with the trade name of 50 BWFS), 5 parts of nylon 1010 (with the trade name of XE4116 BK), 20 parts of POE (with the trade name of DF 810), 10 parts of POE-g-MAH (with the trade name of GR 209), 3 parts of polycarbodiimide (with the content of N = C = N functional groups of 20%, with the trade name of S-7000), 0.1 part of antioxidant 1076 and 0.1 part of antioxidant 168.
The preparation method of the polyamide material comprises the following steps: mixing and drying nylon 66, long-chain nylon, a toughening agent, a hydrolysis resistance agent and an antioxidant according to respective parts by weight, and then preparing polyamide material granules by extrusion, cooling, dehumidification, grain cutting, drying and other preparation processes.
The embodiment also provides an automobile cooling hose taking the polyamide material as a raw material.
The preparation method of the automobile cooling hose comprises the following steps:
drying polyamide material granules for 4 hours at the temperature of 120 ℃, and continuously extruding in an extruder with the screw rotating speed of 2000r/min, wherein the temperature of each continuous extrusion section is respectively as follows: the temperature of the first zone is 220 ℃, the temperature of the second zone is 260 ℃, the temperature of the third zone is 265 ℃, the temperature of the fourth zone is 265 ℃, the temperature of the flange is 270 ℃, the temperature of the machine head is 270 ℃, the temperature of the die is 270 ℃, the automobile cooling hose is obtained by continuously extruding, shaping, cooling and blow-drying, drawing at the speed of 10m/min and cutting.
Example 5
The embodiment provides a polyamide material, and the preparation raw materials of the polyamide material comprise the following components in parts by weight: 80 parts of nylon 66 (with the trade name of 103 FSL), 5 parts of nylon 1010 (with the trade name of RSLC1600BK 385), 20 parts of POE (with the trade name of H-5030S), 10 parts of POE-g-MAH (with the trade name of GR 209), 3 parts of polycarbodiimide (with the content of N = C = N functional group of 20%, with the trade name of S-7000), 0.1 part of antioxidant 1076,0.1 part of antioxidant 168 and 0.5 part of processing aid.
The preparation method of the polyamide material comprises the following steps: mixing and drying nylon 66, long-chain nylon, a toughening agent, a hydrolysis resistance agent, an antioxidant and a processing aid according to respective parts by weight, and then preparing polyamide material granules by extrusion, cooling, dehumidification, grain cutting, drying and other preparation processes.
The embodiment also provides an automobile cooling hose taking the polyamide material as a raw material.
The preparation method of the automobile cooling hose comprises the following steps:
drying polyamide material granules for 8 hours at the temperature of 100 ℃, and continuously extruding in an extruder with the screw rotating speed of 1000r/min, wherein the temperature of each continuous extrusion section is as follows: and the temperature of the first zone is 260 ℃, the temperature of the second zone is 270 ℃, the temperature of the third zone is 275 ℃, the temperature of the fourth zone is 280 ℃, the temperature of the flange is 280 ℃, the temperature of the head is 280 ℃, the temperature of the die is 280 ℃, the automobile cooling hose is obtained by continuously extruding, shaping, cooling and blow-drying, drawing at the speed of 10m/min and cutting.
Example 6
The difference between this example and example 2 is that the parts by weight of POE and POE-g-MAH are 5 parts and 15 parts, respectively (weight ratio 1.
Example 7
The difference between the present example and example 2 is that the parts by weight of POE and POE-g-MAH are respectively 16 parts and 4 parts (weight ratio is 4.
Example 8
The difference between the present example and example 2 is that the parts by weight of POE and POE-g-MAH are respectively 7 parts and 13 parts (weight ratio is 1.
Example 9
The difference between the present example and example 2 is that the parts by weight of POE and POE-g-MAH are 15 parts and 5 parts respectively (weight ratio is 3.
Comparative example 1
This comparative example differs from example 2 in that the toughening agent is POE in an amount of 20 parts by weight, and the polyamide material is prepared by a method which differs from example 2 only in that POE-g-MAH is not added.
Comparative example 2
This comparative example differs from example 2 in that the toughening agent is 20 parts by weight of POE-g-MAH, and the preparation of the polyamide material differs from example 2 only in that no POE is added.
Performance test
Examples 1-9 and comparative examples 1-2 were tested as follows:
(1) Tensile strength: determination of tensile Properties of plastics according to GB/T1040.2-2006 part 2: test conditions for molded and extruded plastics ";
(2) Notched/unnotched impact strength of simply supported beam: according to GB/T1043.1-2008' determination of impact performance of plastic simply supported beam part 1: non-instrumented impact test;
(3) Strength retention (%): the strength retention rate of the PA66 material is improved relative to that of the PA66 material which is not soaked after the PA66 material is soaked in an anti-freezing cooling liquid at Mobil-45 ℃ for 500 hours at the temperature of 100 ℃.
The test results are summarized in table 1.
TABLE 1
The data in the table 1 are analyzed, so that the addition amount of the toughening agent directly influences the toughness of the material, and is reflected in the impact performance of the polyamide material, the notch impact strength of the simple beam made of the polyamide material is over 53.2H, the simple beam does not break under the condition of no notch impact, and the strength retention rate is over 79.8%.
Analysis of comparative examples 1-2 and example 2 revealed that comparative examples 1-2 were inferior to example 2, demonstrating that the combination of POE and POE-g-MAH as tougheners resulted in polyamide materials with better overall properties.
Analysis of example 1 with examples 2 and 3 reveals that example 1 has slightly inferior properties to examples 2 and 3, demonstrating that the starting materials for the preparation of the polyamide material have better properties within the preferred formulation range.
Analysis of examples 6-9 with example 2 revealed that examples 6-7 are inferior to examples 2 and 8-9, demonstrating a better combination of properties for the polyamide materials obtained with a POE and POE-g-MAH weight ratio in the range 1.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (23)
1. The polyamide material is characterized by comprising the following raw materials in parts by weight: 60-80 parts of nylon 66,5-10 parts of long-chain nylon, 10-30 parts of toughening agent, 0.5-3 parts of hydrolysis resistance agent and 0.1-2 parts of auxiliary agent;
the toughening agent comprises a combination of an ethylene-1-octene copolymer and a maleic anhydride grafted ethylene-1-octene copolymer;
the weight ratio of the ethylene-1-octene copolymer to the maleic anhydride grafted ethylene-1-octene copolymer is 1;
the hydrolysis resistance agent comprises polycarbodiimide;
the molar content of N = C = N functional groups in the polycarbodiimide is 10% -20%;
the long-chain nylon is any one or the combination of at least two of nylon 11, nylon 612, nylon 12 or nylon 1010.
2. Polyamide material according to claim 1, characterized in that the auxiliaries comprise antioxidants and/or processing aids.
3. The polyamide material as claimed in claim 2, wherein the antioxidant comprises n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and/or 3- (2, 4-di-tert-butylphenyl) phosphite.
4. The polyamide material as claimed in claim 2, wherein the antioxidant is present in an amount of 0.1 to 1 part by weight.
5. The polyamide material as claimed in claim 2, characterized in that the processing aid is present in an amount of 0.1 to 1 part by weight.
6. The polyamide material as claimed in claim 2, wherein the polyamide material is prepared from the following raw materials in parts by weight: 60-80 parts of nylon 66,5-10 parts of long-chain nylon, 10-30 parts of toughening agent, 0.5-3 parts of hydrolysis resistance agent, 0.1-1 part of antioxidant and 0.1-1 part of processing aid.
7. The polyamide material as claimed in claim 6, wherein the polyamide material is prepared from the following raw materials in parts by weight: 70-75 parts of nylon 66,5-10 parts of long-chain nylon, 12-29 parts of toughening agent, 1.5-2.5 parts of hydrolysis resistance agent, 0.2-1 part of antioxidant and 0.5-1 part of processing aid.
8. The polyamide material as claimed in claim 7, wherein the polyamide material is prepared from the following raw materials in parts by weight: 70-75 parts of nylon 66,5-10 parts of long-chain nylon, 7-15 parts of ethylene-1-octene copolymer, 5-14 parts of maleic anhydride grafted ethylene-1-octene copolymer, 1.5-2.5 parts of hydrolysis resistance agent, 0.1-0.5 part of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, 0.1-0.5 part of 3- (2, 4-di-tert-butylphenyl) phosphite and 0.5-1 part of processing aid.
9. An automotive cooling hose characterized in that a raw material for producing the automotive cooling hose comprises the polyamide material according to any one of claims 1 to 8.
10. A method for manufacturing the automotive cooling hose according to claim 9, comprising the steps of: and drying, continuously extruding, shaping, cooling, blow-drying, drawing and cutting the polyamide material to obtain the cooling hose.
11. The method according to claim 10, wherein the polyamide material is dried at a temperature of 100 to 120 ℃.
12. The method according to claim 10, wherein the polyamide material is dried for a period of 4 to 8 hours.
13. A method of manufacturing as claimed in claim 10 wherein the continuous extrusion is carried out in an extruder.
14. The method of claim 10, wherein the continuous extrusion has a zone temperature of 220-260 ℃.
15. The method of claim 10, wherein the continuous extrusion has a two-zone temperature of 260-270 ℃.
16. The method of claim 10, wherein the continuous extrusion has a three-zone temperature of 265-275 ℃.
17. The method of claim 10, wherein the four zone temperature of the continuous extrusion is from 265 ℃ to 280 ℃.
18. The method of claim 10, wherein the continuous extrusion has a flange temperature of 270 to 280 ℃.
19. The method of claim 10, wherein the continuous extrusion head temperature is 270 to 280 ℃.
20. The method of claim 10, wherein the continuous extrusion is at a die temperature of 270 to 280 ℃.
21. The method of claim 13, wherein the extruder has a screw speed of 1000 to 2000 r/min.
22. The method of claim 10, wherein the drawing is at a rate of 10-20 m/min.
23. The method of claim 10, comprising the steps of:
drying the polyamide material at the temperature of 100-120 ℃ for 4-8h, and continuously extruding in an extruder with the screw rotating speed of 1000-2000r/min, wherein the temperature of each continuous extrusion section is as follows: the temperature of the first zone is 220-260 ℃, the temperature of the second zone is 260-270 ℃, the temperature of the third zone is 265-275 ℃, the temperature of the fourth zone is 265-280 ℃, the temperature of the flange is 270-280 ℃, the temperature of the head is 270-280 ℃, the temperature of the die is 270-280 ℃, the automobile cooling hose is obtained by continuously extruding, shaping, cooling and blow-drying, drawing at the speed of 10-20m/min and cutting.
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